Preparation of aqueous soluble polyamides from renewable succinic acid and citric acid as a new approach to design bio‐inspired polymers

A novel type of aqueous soluble polyamides were prepared as renewable substitutes for ecologically benign poly(aspartic acid) by polymerization of succinic acid ester and hexamethylene diamine in the presence of citric acid ester. The copolymerization resulted in the formation of poly(amide imide) intermediates, which were hydrolyzed to aqueous solutions of polyamides. The hydrolyzed products were confirmed to be copolymers of succinamide and citramide with COOH side chains, similar to poly(aspartic acid). The polyamides showed strong chelating abilities to Ca²⁺ and Pb²⁺ metals, comparable to poly(aspartic acid). Interestingly, they also demonstrated antifreeze activities in water by reducing the ice fractions. The polyamides represent a new class of metal chelators and antifreeze protein mimics derived from succinamide and citramide. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39807.     

Crystalline structure and crystallization of stereoisomeric polyamides derived from arabinaric acid

The pair of stereoisomeric polyamides PA-6dAr and PA-6lAr, as well as the racemic stereocopolyamide PA-6dlAr was synthesized from hexamethylenediamine and 2,3,4-tri-O-methyl-arabinaric acid (d, l and their equimolar mixture, respectively). All these polyamides were aregic, thermally stable and display high crystallinity. The combined analysis by X-ray and electron diffraction revealed that the all three polyamides adopted the same crystal structure, which consists of a rhombic lattice with the chains in a highly contracted conformation capable of accommodating efficiently the sugar moiety in the space. The Avrami kinetic analysis revealed that copolyamide PA-6dlAr crystallized isothermally much slower than the optically homogeneous polyamides. A parallel study carried out on the racemic mixture of PA-6dAr and PA-6lAr evidenced that this mixture has a crystal structure and displays a thermal behavior similar to their separated components, and that its crystallization rate is intermediate between them and the racemic copolyamide PAdlAr.     

Synthesis,characterization, and soil biodegradation study of polyamides derived from the novel bioactive diacid monomer 5‐(2‐phthalimidoethanesulfonamido) isophthalic acid

A new bioactive diacid monomer, 5‐(2‐phthalimidoethanesulfonamido) isophthalic acid ( 6 ), was synthesized in three steps. This monomer can be regarded as biologically active aromatic diacid and may be used in the design of biodegradable and biological materials. This monomer was polymerized with several aromatic diamines by step‐growth polymerization to give a series of biodegradable and highly thermally stable polyamides (PAs) with good yield (70–82%) and moderate inherent viscosity between 0.38–0.68 dL/g in a system of triphenylphosphite/pyridine/N‐methyl‐2‐pyrolidone/CaCl_2. The new aromatic diacid 6 and all of the PAs derived from this diacid and aromatic diamines were characterized by Fourier transform infrared, ¹H‐NMR, ¹³C‐NMR, and elemental analysis techniques. The thermal stability of the PAs was determined by thermogravimetric analysis and differential scanning calorimetry techniques under a nitrogen atmosphere, and we found that they were moderately stable. The soil biodegradability behavior of 6 and all of the PAs derived from this diacid and aromatic diamines were investigated in culture media, and we found that the synthesized diacid 6 and all of the PAs were biodegradable under a natural environmental. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of polyamides from 2,5‐furandicarboxylic acid

The aim of this study is to investigate the synthesis of 2,5‐furandicarboxylic acid (FDCA)‐based copolyamides. Indeed, FDCA monomer may be a potential bio‐based alternative to phthalic acids. A series of polyamides and copolyamides, PA 6‐I(x)/6‐F(y), are synthesized in a pilot scale reactor by melt polycondensation of salts based on FDCA, isophthalic acid (IPA), and 1,6‐hexamethylenediamine. The chemical structure and composition of the resulting copolymers are extensively characterized by NMR (¹H, ¹³C, and 2D), MALDI‐TOF as well as size exclusion chromatography and solution viscosimetry. Their thermal properties are studied by differential scanning calorimetry and TGA and also by a molecular modeling technique. It is pointed out that, during the synthesis, FDCA‐rich polymers overcome a massive decarboxylation of FDCA, preventing the production of high molar mass polymers. It is also found that all polymers are amorphous and that the glass transition temperatures decrease as the amount of FDCA in the polymer increases. This is confirmed by the results from molecular dynamics. In addition, it is observed that the copolymers become more hygroscopic when the amount of FDCA in the copolyamides increases. However, the water uptake of PA 6‐I(x)/6‐F(y) with 90 > x > 50 is lower than those of PA6 and PA 66 polyamides. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45901.     

Synthesis and properties of new polyamides based on a hydroxyethyl cinnamide extended from 3,5‐diaminobenzoic acid

A series of new aromatic polyamides containing cinnamide pendent units were prepared from 2′‐(cinnamide)ethyl‐3,5‐diaminobenzoate and various aromatic dicarboxylic acids by the direct polycondensation reaction, with triphenyl phosphite and pyridine as condensing agents. The polyamides were characterized by ¹H NMR, IR, and UV spectroscopy, and gel permeation chromatography. Their thermal stability was studied by thermogravimetric analysis in air, and differential scanning calorimetry. These polymers were readily soluble in polar aprotic solvents and can be cast from their solutions in flexible and tough films. Glass transition temperatures (T_gs) of these polyamides were observed in the range of 225–245°C. Their inherent viscosities varied from 0.77 to 1.12 dL/g that corresponded to weight–average and number–average molecular weights of 39,000–72,700 and 18,800–29,000, respectively. These polymers can be photochemically crosslinked. The photochemical aspects were revealed by means of UV–vis and IR analyses onto thin films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2013–2020, 2007     

Acylated and hydroxylated polyamides derived from l-tartaric acid

A series of polyamides 6,4 were prepared from 1,6-hexanediamine and active esters of 2,3-di-O-acylated l-tartaric acid by polycondensation in solution. Both O-alkoyl and O-benzoyl esters were used as hydroxyl protecting groups. The resulting acylated polytartaramides were found to be semicrystalline polymers with T_m between 100 and 200 °C and T_g slightly above 100 °C. Controlled hydrolysis of the ester side group led to the preparation of poly(hexamethylene l-tartaramide)s with different content in free hydroxyl groups. These polyamides continue being crystalline but their properties largely differ from those displayed by their parent acylated polymers.     

Synthesis of polyamides from substituted fluorene and diamides in the presence of a copper(I) catalyst

2,7‐Dibromo‐9,9‐dioctylfluorene was synthesized by a two‐step reaction from fluorene and n‐octylboromide. This was reacted with benzamide for the preparation of a model compound and with terephthalamide, isophthalamide, and adipamide for the preparation of polyamides in the presence of a mixture of 10 mol % CuI and 20 mol % N,N′‐dimethylethylenediamine as a catalyst and K₂CO₃ as a base. The monomer and the model compound were characterized with Fourier transform infrared, proton nuclear magnetic resonance, and elemental analysis. The prepared polyamides were characterized with Fourier transform infrared, proton nuclear magnetic resonance, differential scanning calorimetry, thermogravimetric analysis, and solubility and viscosity measurements. The obtained polyamides possessed excellent solubility in common organic solvents, and they exhibited inherent viscosities in the range of 0.93–1.19 dL/g. According to the differential scanning calorimetry analysis, the glass‐transition temperatures of the polyamides were in the range of 84–154°C. Thermogravimetric analysis indicated that a 2% weight loss of the polyamides occurred in the temperature range of 218–253°C under a nitrogen atmosphere. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

共缩聚型可溶性耐高温聚芳酰胺合成与表征

采用二胺1，2—二氢—2—(4—氨基苯基)-4—[4—(4—氨基苯氧基)—苯基卜二氮杂萘—1—酮(二胺A)、对苯二胺为共缩聚二胺单体，与对苯二甲酸在Yamazaki膦酰化法聚合体系中，选择直接缩聚法，成功得到高分子量的聚芳酰胺，其特性粘数为0．96～1．44dL／g。以傅里叶变换红外光谱、核磁共振氢谱等分析手段研究了聚合物的结构，利用差示扫描量热法、热失重分析研究了聚合物的耐热性能。结果表明，该系列聚合物具有高的玻璃化转变温度(约为300℃)，氮气氛中5％热失重温度在450℃以上；当二胺A与对苯二胺的物质的量比例为10：0—5：5时，所得聚合物溶解于强极性溶剂。同时，系统研究了影响聚合物特性粘数的诸多因素，从而确定了最佳工艺条件。     

Synthesis and properties of silicon-containing polyamides

A series of aromatic polyamides incorporating silicon together with phenylquinoxaline or with hexafluoroisopropylidene groups has been synthesized by solution polycondensation of a silicon-containing diacid chloride with aromatic diamines having phenylquinoxaline rings or hexafluoroisopropylidene groups. These polymers are easily soluble in polar aprotic solvents, such as N-methylpyrrolidinone and dimethylformamide, and in tetrahydrofurane, and can be solution-cast into thin, transparent films having low dielectric constant, in the range of 3.26 to 3.68. These polymers show high thermal stability with decomposition temperature being above 400°C and glass transition temperature in the range of 236°C to 275°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1533–1538, 1997     

Biologically active polymers. IV. Synthesis and antimicrobial activity of tartaric acid polyamides

New bactericidal polyamides with quaternary ammonium or phosphonium salts were prepared, and their antimicrobial activities were explored. The polyamides were synthesized by the polycondensation of diethyl‐l‐tartrate or chloromethylated diethyl‐l‐tartrate with ethylenediamine in dry absolute ethanol. The polyamides were modified to yield polymers with either quaternary ammonium or phosphonium salts. The polymers were characterized with elemental microanalysis and ¹H‐NMR and IR spectra. The antimicrobial activity of the polymers bearing onium salts was studied against Gram‐negative bacteria (Escherichia coli, Pseudomones aeruginosa, Shigella sp., and Salmonella typhae), Gram‐positive bacteria (Bacillus subtilis and Bacillus cereus), and a fungus (Trichophytum rubrum) by the cut‐plug and viable‐cell‐count methods. Although all the polymers showed high antibacterial activity, some had no antifungal activity. The tributyl phosphonium salt of the polyamide was more effective against both Gram‐negative and Gram‐positive bacteria than the triethyl ammonium and triphenyl phosphonium salts of the polyamide. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4780–4790, 2006     

Synthesis and characterization of novel Schiff‐base polyamides from copper/benzil bisthiosemicarbazone complexes

A new copper‐containing Schiff‐base diamine, benzil bis(thiosemicarbazonato)copper(II) (CuLH₄), was synthesized in two steps from benzil bisthiosemicarbazone (LH₆). The ligand LH₆ and the complex CuLH₄ were characterized with Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. CuLH₄ was used to prepare novel polyamides. The low‐temperature solution polycondensation of the complex CuLH₄ with various aromatic and aliphatic diacid chlorides afforded copper‐containing Schiff‐base polyamides with inherent viscosities of 0.25–0.36 dL/g in N,N‐dimethylformamide (DMF) and 0.75 dL/g in H₂SO₄ at 25°C. The polyamides were generally soluble in a wide range of solvents, such as DMF, N,N‐dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, tetrachloroethane, hexamethylene phosphoramide, N‐methylpyrrolidone, and pyridine. Thermal analysis showed that these polyamides were practically amorphous, decomposed above 270°C, and exhibited 50% weight loss at and above 400°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of some polyamides incorporating modified isophthalic acid units

Some polyamides with side chains were prepared using a direct polycondensation reaction between carboxyl groups from O‐cinnamoyl‐5‐hydroxyisophthalic acid and N‐cinnamoyl‐5‐aminoisophthalic acid and various diisocyanates in the presence of 4‐dimethylaminopyridine, as catalyst, without use of condensing agents. The polymers were characterized by elemental analysis, viscosimetry, spectroscopic and thermal measurements. © 2002 Society of Chemical Industry     

Synthesis of soluble and thermally stable polyamides from diamine containing (quinolin‐8‐yloxy) aniline pendant group

A novel diamine monomer having pendant 4‐(quinolin‐8‐yloxy) aniline group was successfully synthesized via aromatic substitution reaction of 8‐quinolinol with p‐fluoronitrobenzene followed by Pd/C catalyzed hydrazine reduction, amidation reaction between 4‐(quinolin‐8‐yloxy) aniline and 3,5‐dinitrobenzoylcholoride followed by Pd/C catalyzed hydrazine reduction. The diamine monomer was fully characterized by using FTIR, ¹H‐NMR, ¹³C‐NMR, and elemental analysis. The diamine monomer was polymerized with various aromatic and aliphatic dicarboxylic acids to obtain the corresponding polyamides. The polyamides had inherent viscosity in the range of 0.30–0.41 dL/g and exhibited excellent solubility in the polar aprotic solvents such as DMAc, NMP, N,N‐dimethylformamide, Pyridine, and DMSO. The glass transition temperatures (T_g) of the polymers are high (up to 313°C) and the decomposition temperatures (T_i) range between 200 and 370°C, depending on the diacids residue in the polymers backbone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyamides incorporating furan moieties: 4. Synthesis,characterisation and properties of a homologous series

Interfacial polycondensation of 2,2′‐bis[2‐(5‐chloroformylfuryl)]propane with various diamines gave high yields of a novel series of furanic polyamides with high inherent viscosities. The properties of these polymers (T_g, surface energy, crystallinity, thermal stability) were assessed and examined in terms of the role of the specific structure of the bridging group borne by the diamines. Only three polyamides were partially crystalline, whereas all the others were amorphous. Thermogravimetric analysis revealed that thermal decomposition began above 300 °C in all instances. © 2001 Society of Chemical Industry     

Soluble new optically active polyamides derived from 5‐(4‐methyl‐2‐phthalimidylpentanoylamino)isophthalic acid and different diisocyanates under microwave irradiation in molten ionic liquid

Ionic liquids (IL)s have been generating increasing attention over the last decade. ILs were originally introduced as alternative green reaction media owing to their distinctive chemical and physical properties of nonvolatility, nonflammability, thermal stability, and controlled miscibility. In this investigation, 5‐(4‐methyl‐2‐phthalimidyl‐pentanoylamino)isophthalic acid ( 6 ), as a bulky monomer, containing phthalimide and flexible chiral groups, has been synthesized. The direct polycondensation of this diacid monomer with several aromatic and aliphatic diisocyanates, such as 4,4′‐methylenebis(phenyl isocyanate), toluylene‐2,4‐diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, was carried out in tetrabutylammonium bromide as a molten IL in the presence of different catalysts under microwave irradiation as well as conventional heating. The resulting polyamides (PA)s were characterized by FTIR and ¹H NMR spectroscopy, inherent viscosity measurements, thermal and elemental analysis. The obtained PAs showed high yields and moderate inherent viscosities in a range of 0.32–0.57 dL g⁻¹. The PAs were soluble in aprotic polar solvents. Thermogravimetric analysis showed that PAs are thermally stable, 10% weight loss temperatures in excess of 240 and 245°C, and char yields at 600°C in nitrogen higher than 14%. Since toxic and volatile solvent such as NMP was eliminated, this process was safe and green. It is very important to note that, because of high polarizability of ILs, they are very good solvents for absorbing microwaves. The combination of IL and microwave irradiation leads to large reductions in reaction times, very high heating rate with various benefits of the eco‐friendly approach, named green chemistry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel soluble fluorinated aromatic polyamides derived from fluorinated isophthaloyl dichlorides and aromatic diamines

Two series of fluorinated aromatic polyamides derived from two novel monomers, 5-(4-trifluoromethylphenoxy)isophthaloyl dichloride (3FPC) and 5-(3,5-bistrifluoromethyl-phenoxy)isophthaloyl dichloride (6FPC) with various aromatic diamines were synthesized and characterized. Experimental results indicated that the fluorinated aromatic polyamides showed good solubility in many organic solvents. The solubility of the polyamides was affected by the trifluoromethyl substituents and the pendent phenoxy groups in the polymer backbone. The fluorinated polyamides have good thermal stability with the glass transition temperature of 206-285 °C, the temperature at 5% weight loss of 442-460 °C in nitrogen. The polyamide films also exhibited good mechanical properties and excellent electrical and dielectric properties. The fluorinated groups in the polymer backbone have played an important role in the improvement of electrical and dielectric performance of polymer.     

Fluidity improvement of semiaromatic polyamides: Modification with oligomers

Poly(decamethylene terephthalamide) PA10T with different relative viscosities (RV) were successfully produced by the reaction of 1,10‐decanediamine and terephthalic acid through molecular weight regulator benzoic acid (BA). RV was shown to be decreased linearly with increasing BA concentrations and detailed structures of PA10Ts were characterized by ¹³C‐NMR. Fluidity of PA10T with varying molecular weight was tested and low RV PA10Ts were used as modifiers to improve fluidity behaviors of high RV PA10Ts, meanwhile mechanical properties were maintained. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40058.     

Crystallization studies on linear aliphatic polyamides derived from naturally occurring carbohydrates

The thermal behavior of three series of sugar‐derived polyamides (PA‐nSu) made from the arabinaric, mannaric and galactaric acids, respectively, and α,ω‐alkanediamines containing from 6 to 12 methylene units was investigated by DSC supported by polarizing optical microscopy. Crystallization from the melt under both isothermal and nonisothermal conditions was studied in detail. Melting temperatures of PA‐nSu were found to decay steadily with the length of the polymethylene segment. Data registered from isothermally crystallized samples were analyzed by the kinetics Avrami approach, which revealed that crystallization initiated by combination of instantaneous and sporadically nucleation. Crystallization half‐times indicated that “crystallizability” of PA‐nSu increases with the number of methylenes in the diamine unit and decreases with the length of the carbohydrate‐derived unit. Higher crystallinities were attained for polyamides made of shorter aldaric acids. The relation between thermal data and the configuration of the sugar moiety present in PA‐nSu was discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new polyamides derived from 1,3-bis[4-(4-aminophenoxy)phenyl]adamantane

Several new polyamides were synthesized by direct polycondensation of the 1,3-bis[4-(4-aminophenoxy)phenyl]adamantane ( I ) with various dicarboxylic acids. The polyamides had inherent viscosities and number-average molecular weights (M_n) of 0.46–0.96 dL/g and 28,000–109,000, respectively. All polyamides III had good solubilities and were soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and pyridine. Polyamides had tensile strengths of up to 72.3 MPa, elongation to breakage values of up to 10.2%, and initial modulus of up to 2.1 GPa. Their glass transition temperatures were found to be 228–269°C and 252–307°C using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively. The melting temperature of III_f was observed at 318°C using DSC. The temperatures of polyamides III at a 5% weight loss ranged from 395 to 435°C in air and from 400 to 450°C in a N₂ atmosphere. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:315–321, 1998     

Preparation of polyamides containing para-linked dimethylbiphenylene moieties

A series of wholly aromatic polyamides containing 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid (P-DMBA) and 3,4′-dimethylbiphenyl-4,3′-dicarboxylic acid (Q-DMBA) was prepared by the direct polycondensation method using triphenylphosphite and pyridine. Most of the polymers are readily soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), N,N′-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), pyridine (py), and m-cresol and could be cast into tough and flexible films. The solubilities of copolyamides containing P-DMBA and Q-DMBA as acid components were remarkably improved. These were characterized by inherent viscosity, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical spectrometry (DMS) measurements. The glass transition temperatures of these polymers were in the range of 200–300°C and the 5% weight loss temperatures were 430–470°C. Films prepared by casting from polymer solutions exhibited good tensile properties. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:847–853, 1998